JPH02263851A - Flame-resistant polypropylene resin composition - Google Patents

Abstract

PURPOSE:To provide a flame-resistant polypropylene resin composition comprising polyethylene resin, a silane coupling agent and/or an olefinic synthetic rubber, modified poly ammonium phosphate and a specific nitrogen-containing organic compound. CONSTITUTION:A flame-resistant resin composition comprises (A) 5-25wt.% of polyethylene resin (preferably high density polyethylene), (B) B1: 0.3-5wt.% of a silane coupling agent and/or B2: 3-25wt.% of an olefinic synthetic rubber (preferably ethylene-propylene rubber), (C) 12-25wt.% of a (melamine-modified) poly ammonium phosphate, (D) 5-10wt.% of one kind or more of nitrogen- containing organic compounds (preferably the reaction product of ethylene urea with formaldehyde) capable of producing non-firing gaseous products and carbonic residues by pyrolysis when mixed with polypropylene resin and combined with the component C and (E) the residual amount of the polypropylene resin, the total amount of the components (A)-(E) being 100wt.%.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to flame retardant polypropylene resin compositions.

In more detail, it is mainly composed of polypropylene resin, does not generate corrosive or toxic gases, has little deterioration in moldability, has a high degree of flame retardancy when molded, and is suitable for high humidity conditions. The following relates to a flame-retardant polypropylene resin composition from which a molded article with very little bleeding of flame retardant onto the surface of the molded article can be obtained.

Traditionally, polypropylene resin has good processability, chemical resistance,
Because of its good weather resistance, electrical properties, and mechanical strength, it is widely used in various fields such as household electrical products, buildings, interior decoration products, and automobile parts.

(Prior art) Polypropylene resin is originally a resin that easily burns, but as the applications for which it is used expand, polypropylene resin is also required to have performance as a flame retardant material, and the performance requirements are becoming stricter year by year. There is. Various flame-retardant polypropylene resin compositions have been proposed to meet these demands.

For example, JP-A-53-92855, JP-A-54-
29350, JP 54-77658, JP 56-26954, JP 57-81462
As disclosed in Japanese Patent Application Laid-Open No. 60-1) 0738, compositions in which a hydrous inorganic compound (e.g., magnesium hydroxide, aluminum hydroxide, hydrotalcite, etc.) is added to a polypropylene resin, e.g. , polyethylene with a melt index of 0.01 to 2.0/10 minutes, decabromo diphenyl ether (or dodecachlorododecahydromethanodibenzocyclooctene) as disclosed in Japanese Patent Publication No. 55-30739.
and a composition in which one or more inorganic fillers selected from powdered talc, kaolinite, sericite, silica, and diatomaceous earth are added to polypropylene resin, JP-A-52-1
As disclosed in JP-A No. 46452 and JP-A-59-147050, ammonium phosphate (or amine phosphate) and the group >C-0 (or >C-S or >NH) inserted into the cyclic structure are A reaction product between a nitrogen-containing compound and an aldehyde or 1,3.5-
Compositions in which oligomers (or polymers) of triazine derivatives are added to polypropylene resin have been proposed.

However, in a composition in which a hydrous inorganic compound is added to a polypropylene resin, for example, a composition in which magnesium hydroxide is added, a large amount of the hydrous inorganic compound must be added in order to impart a high degree of flame retardancy. , the composition results in a decrease in moldability.

In addition, compositions containing halogen compounds have relatively little deterioration in moldability and can yield molded products with a high degree of flame retardancy, but they do not produce corrosive or toxic gases during processing or combustion. There are drawbacks such as the occurrence of

Also, JP-A-52-146452, JP-A-59-
The flame-retardant polypropylene resin composition disclosed in Publication No. 147050 has relatively little deterioration in molding processability.
Corrosive and toxic gases are rarely generated during processing or combustion.

However, due to the hygroscopic nature of ammonium phosphate (or amine phosphate) in the composition, severe bleeding of ammonium phosphate (or amine phosphate) onto the surface of the molded product occurs under high humidity conditions such as during the rainy season. This has the disadvantage that it cannot be used as an electrically insulating material under high humidity conditions because the electrical resistance value of the molded product is significantly reduced.

(Problem to be Solved by the Invention) The present inventors have discovered a high degree of flame retardancy, that is, the vertical Test based on combustion test (hereinafter UL94)
The flammability rank is 0.8mm in the combustion trial).
(1/32 inch) has a V-O flame retardant wall thickness, does not generate corrosive or toxic gases during processing or combustion, and has little deterioration in moldability. We have conducted extensive research to obtain a flame-retardant polypropylene resin composition that can produce molded products with very little bleeding of flame retardant components onto the surface of the molded product under high humidity conditions, such as at high humidity.

As a result, polyethylene ml in polypropylene resin! ,
Olefin-based synthetic rubber or silane coupling agent (
or both), ammonium polyphosphate or melamine-modified ammonium polyphosphate, and ammonium polyphosphate or melamine-modified ammonium polyphosphate when mixed in polypropylene resins to produce non-flammable gaseous products and carbonaceous residues by thermal decomposition. It has been discovered that the above-mentioned problems can be solved by a composition containing a specific amount of one type or a mixture of two or more types of nitrogen-containing organic compounds, and the present invention has been completed based on this knowledge.

As is clear from the above description, an object of the present invention is to provide a flame-retardant polypropylene resin composition from which a molded article having a high degree of flame retardancy can be obtained, which solves the above-mentioned problems.

(Means for Solving the Problems) The flame-retardant polypropylene resin composition of the present invention has the following three properties.
It has different configurations.

(1) The total of (A) to (l) below is 100% by weight, (^) Polyethylene resin 5 to 25% by weight (B)
Silane cuff pulling agent 0.3-5% by weight (C) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (D) When mixed with polypropylene resin, A mixture of one or more nitrogen-containing organic compounds which, in combination, can give non-flammable gas products and carbonaceous residues upon pyrolysis; 5-10% by weight (E) flame-retardant polypropylene, the remainder being polypropylene resin; Resin composition.

(2) The total of (F) to (J) below is 100% by weight.
As, CF) polyethylene resin 5-25% by weight (G)
Olefin synthetic rubber 3-25% by weight (H) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (1) When mixed with polypropylene resin, in combination with ammonium polyphosphate or melamine-modified ammonium polyphosphate , one or a mixture of two or more nitrogen-containing organic compounds capable of yielding non-flammable gaseous products and carbonaceous residues upon pyrolysis.
5 to 0% by weight (J) A flame-retardant polypropylene resin composition in which the balance is polypropylene resin.

(3) The total of the following (K) to (P) is 100% by weight.
(K) Polyethylene resin 5-25% by weight (L)
Silane cuffing agent 0.3-5% by weight (M) Olefin-based synthetic rubber 3-25% by weight (N) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12-25% by weight (O) When mixed with polypropylene resin a mixture of one or more nitrogen-containing organic compounds which, in combination with ammonium polyphosphate or melamine-modified ammonium polyphosphate, can give non-flammable gaseous products and carbonaceous residues on thermal decomposition;
A flame-retardant polypropylene resin composition in which 5 to 10% by weight (P) and the balance are polypropylene resin.

Further, the present invention provides the above (D), (1), and (O),
A reaction product of ethylene urea and formaldehyde, or a reaction product of ethylene thiourea and formaldehyde, or 1 having a structure represented by the following general formula [I],
3.5- One or two selected from triazine derivatives
It is preferred to use a mixture of more than one species.

(In the formula, X is a morpholino group or a piperidino group 7, Y
is a divalent group of piperazine, and n is an integer of 2 to 50.

) The polypropylene resin used in the present invention includes crystalline propylene homopolymer, propylene as the main component, propylene and ethylene, butene-1, pentene-1, hexene-1,4-methylpentene-1, heptene-1) Examples include a crystalline copolymer with one or more selected from the group of octene-1 and decene-1, or a mixture of two or more of these. In particular, crystalline ethylene-propylene block copolymers are preferred.

The polyethylene resin used in the present invention can be high density polyethylene, medium density polyethylene, or low density polyethylene, but it is desirable to use high density polyethylene in order to prevent a decrease in the rigidity of the molded product.

The blending ratio of the polyethylene resin to the composition is 5 to 2.
5% by weight, preferably 7-20% by weight, particularly preferably 10-20% by weight. If the blending ratio is less than 5% by weight, it will not be possible to achieve V-0 flame retardancy at a wall thickness of 0.8 ohm (1/32 inch) in the UL94 flame test, and if it exceeds 25% by weight, the flame retardance will not be 0. A wall thickness of .8 mm (1/32 inch) is not preferred because it will not be possible to achieve v-0 flame retardancy.

The silane coupling agent used in the present invention has the general formula RR'5iXz (where R is a hydrocarbon group including a vinyl group, a chloro group, an amino group, a mercapto group, etc.),
X is a hydrolyzable organic group, R' is R or X, and each R (when there are two R's) and each X may be different from each other. ) is a silane represented by for example,
Vinyltrimethoxysilane, vinyltriethoxysilane, 3-aminopropyltriexoxysilane, N-(2-aminoethyl)3-aminopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and the like. Among them, it is preferable to use vinyltrimethoxysilane, vinyltriethoxysilane, and 3-mercaptopropyltrimethoxysilane from the viewpoint of preventing the flame retardant from bleeding under high humidity conditions.

The blending ratio of the silane coupling agent is 0.3 to 5% by weight, preferably 0.5 to 3% by weight, particularly preferably 0.5 to 1% by weight, based on the composition. The blending ratio is 0.
If it is less than 3% by weight, the flame retardant will have a poor bleed prevention effect under high humidity conditions, and if it exceeds 5% by weight, it will have a UL9 rating.
4, it is not possible to achieve the flame retardancy of V-O with a wall thickness of 0.8 am (1/32 inch), which is not preferable.

Examples of the olefin-based synthetic rubber used in the present invention include ethylene-propylene rubber, ethylene-propylene-
Diene rubber, ethylene-1-butene rubber, ethylene-vinyl acetate rubber, etc., and among them, ethylene-propylene rubber and ethylene-propylene-diene rubber are preferably used from the viewpoint of maintaining a high degree of flame retardancy.

The blending ratio of the olefin synthetic rubber is 3 to the composition.
~25% by weight, preferably 5-20% by weight, particularly preferably 5-15% by weight. If the blending ratio is less than 3% by weight, the effect of preventing the flame retardant from bleeding under high humidity conditions is poor, and if it exceeds 25% by weight, it becomes too soft and the good mechanical strength and heat resistance inherent to polypropylene are lost. Undesirable.

As the ammonium polyphosphate or melamine-modified ammonium polyphosphate used in the present invention, commercially available products may be used as they are. Examples of commercially available ammonium polyphosphates include Sumisaf P (trade name, manufactured by Sumitomo Chemical Co., Ltd.) and Exol, it 422. (trade name, produced and sold by Hoechst), melamine-modified ammonium polyphosphates include Sumisaf PM (trade name, manufactured by Sumitomo Chemical Co., Ltd.), and E
Examples include xolit462 (trade name, manufactured and sold by Hoechst).

The blending ratio of the ammonium polyphosphate or melamine-modified ammonium polyphosphate is 12 to 25% by weight based on the composition. If the blending ratio' is less than 12% by weight, UL94
V at 0.8 mm (1/32 inch) wall thickness in combustion test
A composition that achieves the flame retardancy of -O cannot be obtained, and 25
Even if it is blended in an amount exceeding that amount by weight, no further effect of improving flame retardancy can be obtained.

The nitrogen-containing organic compounds used in the present invention include the following: When mixed with polypropylene resin in combination with ammonium polyphosphate or melamine-modified ammonium polyphosphate, the nitrogen-containing organic compounds are non-flammable due to ignition or thermal decomposition due to contact with flame, etc. It is a mixture or reaction product of one or more organic compounds that can produce gaseous products (water, carbon dioxide, ammonia, nitrogen, etc.) and carbonaceous residues. Examples of these compounds include ethylene urea, ethylene thiourea, hydantoin, hexahydropyrimidin-2-one, piperazine-3,6-dione, barbic acid, uric acid, dicyandiamide and their reaction products with aldehydes, or piperazine. and diphenyl carbonate, the reaction product of imidazolidin-2-one and diphenyl carbonate, or the oligomer or polymer of 2-piverazinylene-4-morpholino-1,3,5-triazine 2-piperadiene-4-piperidino Examples include oligomers or polymers of -1,3,5-triazine.

Among these, the reaction product of ethylene urea and formaldehyde, the reaction product of ethylene thiourea and formaldehyde, or the following general formula [! ] Oligomers or polymers of 2-biperazinylene-4-morpholino-1,3,5-triazine, which are 1,3,5-) liazine derivatives, and 2-piperadiene-4-piperidino-1,3 , 5-triazine oligomers or polymers are preferred from the viewpoint of maintaining a high degree of flame retardancy.

(In the formula, X is a morpholino group or a piperidino group, Y is a divalent group of piperazine, and n is an integer of 2 to 50.) The blending ratio of the nitrogen-containing organic compound is 5% to the composition.
~10% by weight. If the blending ratio is less than 5% by weight, flame retardancy of 1) v-0 at 32 inch wall thickness cannot be achieved in the υL94 combustion test, which is a high degree of flame retardancy, and if the blending ratio exceeds 10% by weight, However, no further improvement in flame retardancy can be obtained.

In addition, the nitrogen-containing organic compound, the reaction product of the above-mentioned ethylene urea and formaldehyde, or the reaction product of ethylene thiourea and formaldehyde, or 2-
The oligomer or polymer of biperazinylene-4-morpholino-1,3,5-triazine and the oligomer or polymer of 2-biperazinylene-4-piperidino-1,3,5-triazine can be obtained, for example, by the following method.

To obtain the reaction product of ethylene thiourea and formaldehyde, ethylene thiourea is dissolved in water in an amount of 50 g/It, acidified to a pH value of 2 by mixing with a dilute acid (for example sulfuric acid or phosphoric acid) and 90 g/It. Heat to 3℃
An aqueous solution of 7% by weight formaldehyde is added dropwise to the ethylene thiourea solution and CI! Stir vigorously while maintaining the temperature at 90° C. until the molar ratio 0/ethylenethiourea is equal to 2. Filter the precipitate obtained in the form of a very fine powder,
It can be obtained by washing with water and drying. Further, a reaction product of ethylene urea and formaldehyde can also be obtained by the same method as above.

To obtain oligomers or polymers of 2-biverazinylene-4-morpholino-1,3,5-triazine, equimolar amounts of 2,6-cyclo4-morpholino-1,3,5-
Triazine (e.g. 2,6-dichloro-4-morpholino-1,3,5-triazine or 2,6-dipromo-4-morpholino-1,3,5-triazine) and piperazine are combined with an organic or inorganic base (e.g. triethylamine). , tributylamine, sodium glacial oxide, potassium hydroxide, sodium carbonate, etc.) in an inert solvent such as xylene under heating, preferably at the boiling point of the inert solvent, and after the completion of the reaction, the reaction It can be obtained by filtering the mixture to separate and remove by-product salts, washing with boiling water, and drying.

2-pi,verazinylene-4-piperidino-1,3,5-
To obtain oligomers or polymers of triazine,
equimolar 2,6-cyhalo-4-piperidino-1,3,5
- triazine (e.g. 2,6-dichloro-4-piperidino-1,3,5-triazine or 2,6-dipromo-4-piperidino-1,3,5-triazine) and piperazine with an organic or inorganic base (e.g. (triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, etc.) using an inert solvent such as triisopropylbenzene under heat, preferably below the boiling point of the inert solvent, After the reaction is completed, the reaction mixture is filtered to separate and remove by-product salts, and then washed with boiling water and dried.

The composition of the present invention may contain various additives that are normally added to polypropylene resins, such as antioxidants, antistatic agents, lubricants, and pigments.

The flame-retardant polypropylene resin composition of the present invention can be produced, for example, by the following method.

That is, polypropylene resin, the above-mentioned polyethylene resin, olefin-based synthetic rubber or silane coupling agent (or both), ammonium polyphosphate or melamine-modified ammonium polyphosphate (one or a mixture of two or more selected from nitrogen-containing organic compounds) ) and the above-mentioned various additives are placed in a stirring mixing device, such as a Hensel mixer (trade name), a super mixer, or a tumbler mixer, and after stirring and mixing for 1 to 10 minutes, the resulting mixture is rolled, Melt crosstalk temperature 17 by extruder etc.
It can be obtained by melt-kneading at 0 to 220°C and pelletizing.

(Example) The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited thereto.The evaluation method used in the Examples and Comparative Examples is as follows. According to

1) Compliant with the vertical combustion test of Flame Retardant UL Subject 94 (Underwriter Laboratories, Inc.) "Flammation Test of Plastic Materials for Equipment Parts", wall thickness of test piece 0.8 +u+ (1/ 32 inches).

2) Evaluation of bleedability under high humidity conditions A test piece with a length of 95 fl x 95 m x a thickness of 2 cranes was molded using an injection molding machine, and then placed in a constant temperature bath (Tabai) controlled at a temperature of 80°C and humidity of 80%. (manufactured by MFG) and taken out every day. The removed test piece was dried for 2 hours in a constant temperature dryer (manufactured by Sanyo Electric) adjusted to a temperature of 80°C.
After being left in a desiccator at room temperature overnight, the state of flame retardant bleeding on the surface of the test piece was visually observed. Furthermore, the surface electrical resistance value of this test piece was measured using a vibrating volume type microcurrent electrometer (manufactured by Takeda Riken).

Example 1, Comparative Example 1 Ethylene content 8.5% by weight as polypropylene resin
, melt flow rate (temperature 230℃, load 2.16k)
Discharge amount of molten resin in 10 minutes when adding g) 20g
/10 minutes Crystalline ethylene-propylene block copolymer 55% by weight, melt index as polyethylene resin (discharge amount of molten resin in 10 minutes when temperature 190°C and load 2.16 kg is applied) 6.5 g/10 15% by weight of polyethylene (Chisso Polyethylene (trademark) M2B5, manufactured by Chisso ■), 1.0% by weight of vinyltrimethoxysilane (SiLa Ace (trademark) 5210, manufactured by Chisso ■), ammonium polyphosphate (Sumisafe P (trademark)) (manufactured by Kagaku Kogyo ■) 21% by weight, a polymer of 2-biperazinylene-4-morpholino-1,3,5-triazine (n-1) as a nitrogen-containing organic compound, molecular weight approximately 2770)
8% by weight, 2.6-di-t-butyl- as various additives
p-cresol 0.15% by weight, di-myristyl-β,
0.2% by weight of β-thiodibropione) and 0.1% by weight of calcium stearate were placed in a Hensel mixer (trade name) and stirred and mixed for 3 minutes. The resulting mixture was melt-cross-extruded using an extruder with a diameter of 45 at a melt-mixing temperature of 200'C to form pellets.

In addition, as Comparative Example 1, 56% by weight of polypropylene resin
The ingredients were put into a Hensel mixer (trade name) at the mixing ratio according to Example 1, except that no silane coupling agent was added, and the mixture was stirred, mixed by melt extrusion, and pelletized according to Example 1. It became.

Examples 2 to 6 Pelletization was performed in accordance with Example 1, except that the type of silane coupling agent was changed to the silane coupling agent listed in Table 1.

Examples 7 to 9, Comparative Examples 2 to 3 Example 1 except that the blending ratios of the polypropylene resin and silane coupling agent were changed to the blending ratios shown in Table 1.
Pelletized in accordance with.

Example 10 Pelletization was carried out in accordance with Example 1, except that a reaction product of ethylene urea and formaldehyde was used as the nitrogen-containing organic compound.

Example 1), Comparative Examples 4 to 5 Pelletization was performed in accordance with Example 1, except that the blending ratios of polypropylene resin and polyethylene resin were changed to the blending ratios shown in Table 1.

Examples 1-1) Bereftwo 10 obtained in Comparative Examples 1-5
After drying at a temperature of 0°C for 3 hours, the pellets were molded into specified test pieces for flame retardancy and bleedability evaluation using an injection molding machine with the maximum cylinder temperature set at 220''C. The test pieces were used to evaluate flame retardancy and bleedability under high temperature conditions.The results are shown in Table 1.

The symbols in Table 1 are as follows.

Component (A): Polyethylene resin Nisso Seishi 80, Component (B): Bl vinyltrimethoxysilane,
at 3-aminopropyltriethoxysilane, B3
3-methacryloxypropyltriethoxysilane, Bh 3-glycidoxypropyltrimethoxysilane, B, 3-chloropropyltrimethoxysilane, Bh
3-mercaptopropyltrimethoxysilane, component (C): ammonium polyphosphate, component (D): DI 2-biverazinylene-4-
Polymer of morpholino-1,3,5-triazine (n=
1)), 0□ Reaction product of ethylene urea and formaldehyde, Component (E): As polypropylene resin, ethylene-propylene block copolymer (ethylene content 8.5% by weight, melt index 20g/
10 minutes), *1 Surface resistance value before humidification treatment: Surface electrical resistance value before exposure in a heated and humidified atmosphere, *2 Surface resistance value after 7 days of humidification treatment: Temperature 80°C Humidity 8
Surface electrical resistance value after 7 days of exposure at 0% *3 Unable to evaluate: The test piece burned and flame retardancy could not be evaluated.

From Table 1, it can be seen that by blending the silane coupling agent, the bleeding property under high temperature and high humidity conditions is improved, and the blending ratio of the silane cuffing agent is preferably 0.3 to 5% by weight.

Example 12, Comparative Example 6 Ethylene content 18.5% by weight as polypropylene resin
, melt flow rate (temperature 230℃, load 2.16k)
Discharge amount of molten resin for 10 minutes when adding g) 20
g / 10 minutes Crystalline ethylene-propylene block copolymer 51% by weight, melt index as polyethylene resin (discharge amount of molten resin in 10 minutes when temperature 190°C and load 2.16 kg is applied) 6.5 g / 10% by weight of 10-minute polyethylene (Chisso Polyethylene (trademark) M2B5, manufactured by Chisso ■), 10% by weight of ethylene-propylene rubber (EP-02P, manufactured by Japan Synthetic Rubber ■) as an olefinic synthetic rubber, ammonium polyphosphate (Sumisafe P) (trademark) manufactured by Sumima Kagaku Kogyo ■) 21% by weight, a polymer of 2-biperazinylene-4-morpholino-1,3,5-triazine (n = 1) as a nitrogen-containing organic compound, molecular weight approximately 2,770) 8% by weight, 2. As various additives.
6-di-t-butyl-p-cresol 0.15% by weight,
Di-myristyl-β,β-thiodipropionate 0.2
% by weight and 0.1% by weight of calcium stearate were placed in a Hensel mixer (trade name) and stirred and mixed for 3 minutes. The resulting mixture was melt-cross-extruded using an extruder with a diameter of 45 mm at a melt-mixing temperature of 200° C. to form pellets.

In addition, as Comparative Example 6, 61% by weight of polypropylene resin
Except for binding and not containing ethylene-propylene rubber,
Each of the ingredients was put into a Hensel mixer (trade name) at the mixing ratio according to Example 12, and mixed by stirring, melt-kneaded and extruded, and pelletized according to Example 12.

Examples 13-14, Comparative Example 7 Example 1 except that the blending ratios of polypropylene resin and ethylene-propylene resin were changed to the blending ratios shown in Table 2.
It was pelletized according to 2.

Comparative Example 8 Pelletization was carried out in accordance with Example 12, except that the blending ratios of polypropylene resin and polyethylene resin were changed to the blending ratios shown in Table 2.

After drying the pellets obtained in Examples 12 to 14 and Comparative Examples 6 to 8 for 3 hours at a temperature of 100°C, the pellets were used to mold flame retardants using an injection molding machine with the maximum temperature of the cylinder set at 220°C. , and predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature conditions were evaluated. The results are shown in Table 2.

From Table 2, by blending ethylene-propylene rubber, the bleedability under high temperature and high humidity conditions is improved.
The blending ratio of ethylene-propylene rubber is 5 to 25% by weight.
It turns out that is preferable.

Table 2 The symbols in Table 2 are as follows.

Component (F): Polyethylene resin Nisso ■% M2B5
, Component (G): Ethylene-propylene rubber manufactured by Japan Synthetic Rubber ■ EP-02P, Component (H): Ammonium polyphosphate, Component (1): 2-piperadiene-4-morpholino-! , 3.5-triazine poly? -(n=1))
, Component (J): As a polypropylene resin, ethylene-
Propylene block copolymer (ethylene content 8.5% by weight, melt index 20g/
10 minutes), *1, *2, *3 are the same as the symbols in Table 1 above.

Example 15, Comparative Example 9 Ethylene content 18.5% by weight as polypropylene resin
, melt flow rate (temperature 230℃, load 2.16k)
Discharge amount of molten resin for 10 minutes when adding g) 20
g/10 minutes crystalline ethylene-propylene block copolymer 50% by weight, melt index as polyethylene resin (amount of molten resin discharged in 10 minutes when temperature 190°C and load 2.16 kg is applied) 6.5 g /1
0 minute polyethylene (Chisso Polyethylene (trademark) M2B
5° Chisso Special) 10% by weight, ethylene-propylene rubber (EP-02P, Japan Synthetic Rubber Special) 10% by weight as an olefinic synthetic rubber, vinyltrimethoxysilane (Sila Ace (trademark) 5 as a silane coupling agent)
210, Chisso special product) 1.0% by weight, ammonium polyphosphate (Sumisafe P (trademark) manufactured by Sumitomo Chemical Industry ■) 21% by weight, 2-biperazinylene-4-morpholino-! as a nitrogen-containing organic compound. , 3.5-triazine polymer (
n=1), molecular weight approximately 2.770) 8% by weight, 2.6-di-t-butyl-p-cresol 0.1 as various additives
5% by weight, 0.2% by weight of di-myristyl-β, β-thiodipropionate and 0.1% by weight of calcium stearate.
% by weight was placed in a Hensel mixer (trade name) and stirred for 3 minutes.

The obtained mixture was melt-kneaded using an extruder with a diameter of 45 at a temperature of 2.
The mixture was melt-kneaded and extruded at 00°C to form pellets.

In addition, as Comparative Example 9, 61% by weight of polypropylene resin
The ingredients were placed in a Hensel mixer (trade name) at the mixing ratios in accordance with Example 15, except that the binding, ethylene-propylene rubber, and silane coupling agent were not blended, and the mixture was stirred and mixed in accordance with Example 15. , melt kneading extrusion,
Pelleted.

Examples 16-22, Comparative Examples 10-12 Pelletization was performed according to Example 15, except that the blending ratios of polypropylene resin, ethylene-propylene rubber, and silane coupling agent were changed to the blending ratios shown in Table 3. .

Comparative Example 13 Pelletization was performed in accordance with Example 15, except that the blending ratios of polypropylene resin and polyethylene resin were changed to the blending ratios shown in Table 3.

The pellets obtained in Examples 15 to 22 and Comparative Examples 9 to I3 were dried at a temperature of 100°C for 3 hours, and then flame retardant was tested using the pellets in an injection molding machine with the maximum temperature of the cylinder set at 220°C. , and predetermined test pieces for evaluation of bleedability were molded. Using this test piece, flame retardancy and bleedability under high temperature conditions were evaluated. The result is the third
Shown in the table.

The symbols in Table 3 are as follows.

Ingredient (K): Polyethylene resin M680 manufactured by Chisso ■,
Component (S): Vinyltrimethoxysilane, Component (M)
: Ethylene-propylene rubber Made by Japan Synthetic Rubber E
P-02P.

Component (N) = ammonium polyphosphate, Component (O): 2-biverazinylene-4-morpholino-1,3,5-triazine polymer (n-1))
, Component (P): As a polypropylene resin, ethylene-
Propylene block copolymer (ethylene content 8.5% by weight, melt index 20g/
10 minutes), *1, *2, *3 are the same as the symbols in Table 1 above.

From Table 3, it can be seen that even when both the silane coupling agent and the ethylene-propylene rubber are used in combination, the bleeding property under high temperature and high humidity conditions is improved.

(Effects of the Invention) The composition of the present invention exhibits very little bleeding to the surface of molded products under high humidity conditions and has a high degree of flame retardancy, that is, UL9
4 In the combustion test, molded products with a wall thickness of 0.8 sum (1/32 inch) have a flame retardancy of ■-0, and do not generate corrosive or toxic gases during processing or combustion. It is a flame-retardant polypropylene resin composition that can be suitably used in the production of secondary buildings, interior decorations, parts for household electrical appliances, parts for automobiles, etc.

Procedural amendment June 14, 1989

Claims (7)

[Claims] (1) The total of the following (A) to (E) is 100% by weight.
(A) 5-25% by weight of polyethylene resin (B) 0.3-5% by weight of silane coupling agent (C) 12-25% by weight of ammonium polyphosphate or melamine-modified ammonium polyphosphate (D) Mixed with polypropylene resin 5 to 10 mixtures of one or more nitrogen-containing organic compounds which, when combined with ammonium polyphosphate or melamine-modified ammonium polyphosphate, can give non-flammable gaseous products and carbonaceous residues on thermal decomposition. Weight % (B) A flame-retardant polypropylene resin composition in which the remainder is polypropylene resin. (2) The total of (F) to (J) below is 100% by weight.
(F) 5-25% by weight of polyethylene resin (G) 3-25% by weight of olefinic synthetic rubber (H) 12-25% by weight of ammonium polyphosphate or melamine-modified ammonium polyphosphate (I) Mixed with polypropylene resin 5-10% by weight of one or more nitrogen-containing organic compounds capable of giving non-flammable gaseous products and carbonaceous residues on thermal decomposition, if in combination with ammonium polyphosphates or melamine-modified ammonium polyphosphates; (J) A flame-retardant polypropylene resin composition in which the remainder is polypropylene resin. (3) The total of the following (K) to (P) is 100% by weight.
(K) 5-25% by weight of polyethylene resin (L) 0.3-5% by weight of silane coupling agent (M) 3-25% by weight of olefinic synthetic rubber (N) Ammonium polyphosphate or melamine-modified ammonium polyphosphate 12
~25% by weight (O) of nitrogen-containing organic compounds which, when mixed with polypropylene resins, can give non-flammable gas products and carbonaceous residues upon thermal decomposition in combination with ammonium polyphosphates or melamine-modified ammonium polyphosphates. 5 to 10% by weight of one type or a mixture of two or more types (P) A flame-retardant polypropylene resin composition in which the remainder is polypropylene resin. (4) As (D) of claim 1, a reaction product of ethylene urea and formaldehyde, a reaction product of ethylene thiourea and formaldehyde, or the following general formula [
A flame-retardant polypropylene resin composition using one or a mixture of two or more selected from 1,3,5-triazine derivatives having the structure represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is an integer from 2 to 50.) (5) As (I) of claim 2, the reaction product of ethylene urea and formaldehyde, or the reaction product of ethylene thiourea and formaldehyde, or the following general formula [
A flame-retardant polypropylene resin composition using one or a mixture of two or more selected from 1,3,5-triazine derivatives having the structure represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is an integer from 2 to 50.) (6) (O) of claim 3 is a reaction product of ethylene urea and formaldehyde, or a reaction product of ethylene thiourea and formaldehyde, or the following general formula [
A flame-retardant polypropylene resin composition using one or a mixture of two or more selected from 1,3,5-triazine derivatives having the structure represented by [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, X is a morpholino group or piperidino group, Y is a divalent group of piperazine, and n is an integer from 2 to 50.) (7) As polypropylene resin, crystalline propylene homopolymer, propylene as main component, propylene and ethylene, butene-1, pentene-1, hexene-1,4-
Claims 1 to 6 in which a crystalline copolymer with one or more selected from methylpentene-1, heptene-1, octene-1, and decene-1 or a mixture of two or more of these is used.
The flame-retardant polypropylene resin composition according to any one of the above.